Method and form for manufacturing rubber goods fom an aqueous dis persion of rubbfr



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M Apr. z, 1935 METHOD AND FORM FOR MANUFACTURING RUBBER GOODS FROM AN AQUEOUS DIS PERSION OF RUBBER Douglas Frank Twiss, Wylde Green, England, assigner to American Anode Incorporated, Akron, Ohio, a corporation of Delaware No Drawing.

Serial No. 517,099. 22, 1926 38 Claims.

This invention relates to the manufacture of articles of rubber or the like directly from the latex or from similar aqueous dispersions containing the rubber or other like substance.

The objects of this invention include the manufacture of articles or coatings by a process of direct coagulation of rubber from an aqueous dispersion therof on the surface of a form, and

particularly such manufacture by an improved process whereby the coagulatigrrof the rubber is effected in an economical, readily controlled process involving the minimum of manipulation.

This invention consists broadly in coating an impervious form with a film of a liquid coagulant, and thereafter associating the coagulant-coated form with an aqueous dispersion of rubber or the like, the rubber being coagulated as a firm, coherent layer on the surface of the form. The coagulant film should preferably have a consistency great enough to prevent any appreciable displacement of the coagulant during'the handling of the form prior to its association with the rubber dispersion or during its actual contact therewith. This increased consistency of the coagulant may, for example, be effected by cooling it. In one embodiment of the invention the consistency'of the coagulant film is increased to the point of solidification by supercooling, or gelation, or even complete crystallization by lowering its temperature before the form is immersed in the latex or other dispersion. However, it is preferred to avoid crystallization of the coagulant, for a crystallized film is not as homogeneous and does not possess as smooth a surface as a non-crystalline film.

The forms or bases employed in the practice of this invention may be made of any substance which is impervious to water and to the particular coagulant which is employed. Forms of glass, glazed porcelain, stainless steel, or aluminum are particularly suitable for the manufacture of ordinary rubber articles which are to be stripped from the forms, although other compositions such as wood, molded plastics, or even hard or soft vulcanized rubber,'may sometimes be employed. Permanent coatings of soft or hard rubber are readily applied by the method of this invention to articles of wood, metal, etc., of simple or intricate shape, the said articles preferably being first coated with a suitable adhesive which is impervious to water and to the coagulant.

The coagulants may be pure liquid acids or coagulating salts, or solutions of solid or liquid acids or salts in water or other appropriate solvents, or mixtures of several coagulants. For example, pure formic, acetic or lactic acid, or solu- Application February 19, 1931, In Great Britain October tions of these acids or of other strong organic acids such as oxalic, malonic or citric acid, or of the non-oxidizing mineral acids such as hydrochloric, sulphuric or phosphoric acids, may be employed as coagulants.

If it is preferred to employ a substantially neutral coagulant, solutions of polyvalent metal salts such as calcium chloride, calcium lactate, calcium nitrate, calcium perchlorate, magnesium, chloride, magnesium sulphate, aluminum sulphate, cadmium sulphate, lead acetate zinc chloride, or zinc sulphate are suitable; whereas if an acid coagulant is preferred, any of the above-mentioned salts may be mixed with a solution of an acid, which does not react therewith to form insoluble or otherwise undesirable products, or an acid salt such as alum, sodium dihydrogen phosphate, or sodium hydrogen sulphate may be substituted therefor.

Coagulants which are only sparingly soluble, such ascalcium sulphate or sodium silicofluoride, may likewise be employed, being suspended in a finely divided condition in a liquid medium, either with or without the addition of other more soluble coagulants.

The forms are coated with the liquid coagulants by any suitable means, such as spraying or brushing, although dipping in a bath of the liquid is ordinarily preferred because of its greater simplicity. If necessary, any excess coagulant, such as drops collecting on the lower portion of the form, may be removed by wiping, or distributed uniformly over the surface by inverting the form or rotating it about a horizontal axis.

The alternativeembodiment of this invention, in which the coagulant film is' solidified or con gealed before the form is dipped in the latex or other equivalent dispersion, has advantages which sometimes outweigh the advantage of simplicity of operation of the permanently liquid coagulants enumerated above. In particular, the solidified coagulant film is not subject to flow. so that the thickness is maintained uniform, and so that the coagulant is not subject to displacement through contact with the rubber dispersion.

Such congealable coagulants include acids and coagulating salts which are solid at normal temperatures, but which melt at relatively low temperatures, preferably below the boiling point of water. For example, the following substances each of which has a melting point between C. and 100 C. may be employed: glacial phosphoric acid, selenic acid, trichloracetic acid, benhydrogen phosphate, or hydrated salts which melt or mixtures of such substances may be employed.

These coagulants are maintained in a molten condition, the form being dipped in the liquid coagulant to provide it with a surface film of the coagulant, and'thereafter being permitted to cool in order that the coagulant may solidify before the form is dipped in the latex. When the compositionof the coagulant'is-properly chosen, it will solidify to a smooth, glassy film instead of crystallizing.

Inanother modification of the invention the coagulant is incorporated in a composition which is liquid at temperatures somewhat above the normal, but sets to a gel when it is cooled. For

example, any of the coagulants mentioned abovev may be incorporated ina warm or hot solution of gelatine, agar-agar, or other gelatinous, colloid in any proportions which will not inhibit gelationof the mixture. The soluble salts of the poly-' valent metals such as calcium, magnesium, zinc, or aluminum are preferred, but acid salts or the ,acids themselves may be employed if the concentration of the respective constituents of the mixture are so adjusted that the acid does no prevent the gelation of the colloid. The forms are coated with these coagulant gels by immersing them in the heated, liquid composition and cooling them after withdrawal, until the coagulant composition sets to a gel. It-is even possible to coat the forms with a film 'of a solution of sodium silicate (water glass), and to treat the liquid film with a strong acid such as a solution of sulphuric acid. The film of sddium silicate solution is thereby converted to a gel of colloidal silicic acid containing free sulphuric acid absorbed therein the free acid being the active coagulant.

(incorporated in widely varying proportions, be-

ing preferably finely suspended in an aqueous medium before they are added to the dispersion of rubber. The dispersion may have any desired rubber content within such limits that a firm, coherent, well coagulated deposit is produced therefrom, but is preferably rather concentrated, a concentration of about 50 to of dispersed constituents, including the rubber, being preferred. The more concentrated dispersions have the advantages of giving rise to more firmly coagulated deposits, and of containing less moisture which must subsequently be eliminated from the deposits by evaporation. If desired, ingredients such as common salt, sodium sulphate, or calcium sulphate, which have an incipient coagulating effect on the rubber dispersions may be added.

As a specific example of one embodiment of the invention, shaped articles such as tobacco pouches, bath caps, fountain pen sacs, etc., are made on molds of metal or glazed porcelain by dipping the molds in a concentrated aqueous solution of calcium chiorldeand wiping 0d the excess of the liquid. The forms with a film of coagulant on the surface are then dipped in a The coagulant, diil'using out into the latex from the film on the surface of the form, coagulates a uniform layer or the rubber composi-' tion. The form is removed from the latex after about five minutes, the coagulated rubber is dried, vulcanized and stripped from the form. If a greater thickness of rubber is desired, the form is'left in the latex for a longer period of time, and if a thiner deposit is desired, it is removed sooner.

In the manufacture of high grade rubber gloves such as are used for protection against acids, the forms of glazed porcelain in the shape of hands are immersed in a bath of molten calcium nitrate (Ca(NOa) 2.4HzO). This salt melts and dissolves in its water ofcrystallization at about 42 C., but is preferably maintained at a slightly higher temperature, say between 50 C. and 60 C.,.by means of a hot water or steam Jacket surrounding the coagulant bath. The form maybe somewhat prewarmed before it is dipped in the coagulant, to prevent the coagula'nt from congealing immediately on the surface of the form. h After the form is removed from the coagulant it is inverted or is rotated about a horizontal axis in order to effect a uniform distribution of the liquid coagulant on the surface of the form before it cools and solidifies.

The form with the film of solidified coagulant on the surface is then immersed in a vulcanizable latex which may be prepared by mixing the quantity of concentrated, ammonia-preservedlatex which contains 100 parts by weight of rubber with dispersions containing 10 parts zinc oxide, 3 parts sulphur, 0.5 part organic accelerator, and 1 part lampblack, the completed mixture containing about 50% water. The form is left in this latex composition for about 10 minutes, and is then removed with a uniform deposit of coagulated rubber on the surface. The deposits are washed in running water, dried, vulcanized, and stripped from the forms.

As an example oi another embodiment of the invention, a football bladder is made in one piece on a suitably shaped form of hollow metal, a hole being left in the rubber for extracting the form and the hole being subsequently sealed by a patch containing the tube for inflating the bladder. The form is .dipped in a solution of 10% of calcium nitrate and 1% of agar-agar in water, the solution being maintained at a temthe'formis then washed, dried, vulcanized and finished in the usual manner.

such as one 'of thelatex compositions described above. If it is desired, the proportion of sulphur in the latex composition may be increased. so that the coating may be vulcanized to hard rubber. The coagulated rubber coating on the articles is dried and vulcanized, the vulcanization preferably being carried out under a high pressure which is maintained until the vulcanization is complete and the article cooled, in order to minimize the chance of blisters forming between the rubber and the metal.

This application ,is a continuation in part of my copending applications Serial No. 220,845, filed September 20, 1927, and Serial No. 294,317, filed July 20, 1928 While I have herein disclosed with considerable particularity certain preferred manners of performing my invention, I do not thereby desire or intend to limitmysclf solely thereto, for, as hitherto stated, the procedure may be modified, the precise proportions of the materials utilized may be varied, and other materials having equivalent properties ;may be employed if desired without departing from the spirit and scope of the invention as defined in the appended claims.

I claim:

1. The method of manufacturing shaped articles from an aqueous dispersion of an organic substance which comprises applying to 'the surface of an impervious form a thin layer of a coagulant for the dispersion, and associating the coated form with the dispersion until the coague lum has attained the desired thickness.

2. The method of producing shaped rubber articles which comprises coating an impervious form with a film of coagulant and associating the coated form with an aqueous rubber dispersion until the coagulum has attained the desired thickness.

3. The method of' producing shaped rubber articles which comprises coating an impervious form with a film of a solid coagulant adapted to dissolve in an aqueous medium with the liberation of coagulating ions, and immersing the coated form in an aqueous rubber dispersion.

4. The method of producing shaped rubber articles which comprises coating an impervious form with a film of a soluble salt adapted to liberate polyvalent metallic ions, and immersing the coated form in an aqueous dispersion of rubber.

5. The method which comprises coating on impervious base with a liquid film of a coagulant, and associating the coated base with a coagulable dispersion of rubber.

6. The method which comprises coating an impervious base with a liquid film of a coagulant, and immersing the coated base in an aqueous dispersion of rubber.

7. The method which comprises dipping an impervious base in a liquid coagulant, immersing the coated base in an aqueous dispersion of rubher until an appreciable thickness of rubber is coagulated thereon, and drying the deposited rubber. 4

8. The method which comprises coating animpervious base with a liquid film comprising a coagulant, congealing the liquid film by lowering its temperature, and associating the coated base with an aqueous dispersion of rubber.

"9. The method which comprises coating an impervious base with a liquid film of a composition comprising a coagulant, which composition is solid at normal temperatures, but is liquid at somewhat elevated temperatures, congealing the liquid film by lowering its temperature, and immersing the coated base in an aqueous dispersion of rubber.

10. A method as .in claim'9, in which the coagulant is a salt of a polyvalent metal.

11. The method which comprises coating-an impervious base with a liquid film of a composition comprising .a coagulant, which composition is a hard, glassy solid at normal temperatures, but is liquid at somewhat elevated temperatures, congealing the liquid film by lowering its temperature, and immersing the coated base in an aqueous dispersion of rubber.

12. The method which comprises dipping an impervious base in a molten bath of a composition comprising a coagulant, which composition is a hard, glassysolid at normal temperatures, but is liquid at somewhat elevated temperatures, congealing the coating thus formed by lowering its temperature, immersing the coated base in an aqueous dispersion of rubber until an appreciable thickness of rubber is coagulated thereon, and drying the eoagulated rubber.

13. The method which comprises coating an impervious form with a liquid film of a composition comprising a coagulant and a gel-forming colloid causing the liquid film to gel, and immersing the coated base in an aqueous dispersion of rubber.

14. The method which comprises dipping an impervious basein a liquid composition comprising a coagulant and a gel-forming colloid, gelling the coating thus formed by lowering its temperature, immersing the coatcd'base in an aqueous dispersion of rubber until an appreciable thickness of rubber is coagulated thereon, and drying the coagulated rubber.

15. The method which comprises dipping an impervious base in a liquid composition comprising a salt of a polyvalent metal and a gel-forming colloid, gelling the coating thus formed by lower ing its temperature, immersing the coated base in a vulcanizable latex until an appreciable thickness of rubber is coagulated thereon, and drying and vulcanizing the coagulated rubber.

16. The method which comprises coating an impervious base with a liquid film of a coagulant. increasing the consistency of the coagulant, and associating the coated base with an aqueous dispersion of rubber.

17. The method which comprises coating an impervious base with a. liquid film of a coagulant, increasing the consistency of the coagulant to a point at which substantially no flow occurs in the film, and immersing the coated base in an aqueous dispersion of rubber.

18. The method which comprises coating an impervious base with a liquid film of a coagulant, solidifying the coagulant film, and immersing the coated base in an aqueous dispersion of rubber.

1.9. The method which comprises coating an imperivous base with a'liquid film of a coagulant. causing the coagulant to gel, and immersing the coated base in an aqueous dispersion of rubber.

20. The method which comprises providing an ,from a rubber dispersion,

impervious base with a coating of a film of a solid gel comprising a coagulant, and immersing the coated base in an aqueous dispersion of rubber.

21=A form for depositing dispersed materials which comprises an impervious base with a surface of a substantially non-fiowable coagulant material. I

22. A form for depositing dispersed materials from a rubber dispersion, which comprises a surface of a solidified coagulant composition.

23. A form for depositing dispersed materials from a rubber dispersion, which comprises-an impervious base and a film of substantially nonfiowable coagulant material thereon. v

24. A form for depositing dispersed materials from a rubber dispersion, which comprises an 3 impervious base .and a liquid film containing a coagulant salt thereon.

' V 25.. A form for depositing dispersed materials from a rubber dispersion, which comprises a surface of a solid coagulant gel.

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26. A form for depositing dispersed material from a rubber dispersion; which comprises a vitreous surface of coagulant material.

2'7. A form for depositing dispersed materia from a rubber dispersion, which comprises a vitreous surface of coagulant salts.

28. The method which comprises coating an impervious form with a liquid film comprisinga coagulant, increasing the consistency of theliquid film, immersing the coated form in an' aqueous dispersion of rubber until a layer of rub- 30(The method which comprises coating an impervious form with a liquid film o! a coagu-.

lant composition, increasing the consistency of the coagulant to a point at which substantially no fiow occurs in the film, immersing the coated form in a vulcanizable aqueous dispersion of rub-- ber until a layer of rubber of the desired thickness is coagulated thereon, drying and vulcanizing the coagulated rubber, and removing it from the form.

31. In the herein described method of manufacturing rubber goods, the steps which com- -prise coating the surface of an impervious mold with a gel containing a rubber coagulant, and immersing the treated mold in an aqueous dispersion of rubber for such time as to build up thereon a layer of coagulated rubber.

32. In the herein described method of manufacturing rubber goods, the steps-which comprise coating a'surfa ce of animpervious mold with a gel containing, a saline coagulant, and immersing 33. In the herein described method of'manufac turing rubber goods, the steps which comprise coating a surface of an impervious mold with aliquid containing a rubber coagulant, causing the liquid to gel, and immersing the mold with its coated surface in contact with an aqueous dispersion of rubber for suchtime as to build up on the coated surface a layerof coagulated rubber.

34. In the herein described method of manufacturing rubber goods, the steps which comprise coating the outer surface ,of a water insoluble, water-impermeable mold with a gel containing a rubber coagulant, and immersing'the treated mold in an aqueous dispersion of rubber for such time as to build up thereon a layer of coagulated rubber. v

35. In the herein described method-of manufacturing rubber goods, the steps which comprise coating the outer surface of an impervious mold with a gel containing a rubber coagulant, selected from a class comprising salts of polyvalent metals, and immersing the treated mold in an aqueous dispersion of rubber for such time as to build up thereon a layer of coagulated rubber.

36. In the herein described method of manufiuoride and immersing the mold with its coated surface in contact with an aqueous dispersion of rubber for such time as to build up on the coated surface a layer of coagulated rubber.

3'7. The method of manufacturing shaped articles from an aqueous dispersion of rubber which comprises coating a form with a layer of a gel containing a coagulant, immersing the coated form in an aqueous dispersion of rubber until a deposit of rubber of the desired thickness is coagulated thereon, and removing the deposited rubber from the form.

38. The method of manufacturing shaped articles from an aqueous dispersion of rubber which comprises coating a form witha layer of a gel containing a coagulant, immersing the coated form in an aqueous dispersion of rubber until a deposit of rubber of the desired thickness is coagulated thereon, drying the deposited rubber, and removing it from the form.

DOUGLAS FRANK TWISS. 

